Process for preparing hexadecahedral decaborane derivatives and resulting products



United States Patent "ice 3,395,171 PROCESS FOR PREPARING HEXADECAHEDRALDECABORANE DERIVATIVES AND RESULT- ING PRODUCTS William C. Drinkard,Jr., Wilmington, Del., assignor to E. I. du Pont de Nemours and Company,Wilmington, Del., a corporation of Delaware No Drawing.Continuation-in-part of application Ser. No. 220,909, Aug. 31, 1962.This application June 30, 1965, Ser. No. 468,565

12 Claims. (Cl. 260462) ABSTRACT OF THE DISCLOSURE A process forpreparing derivatives of hexadecahedral decaborane by reacting an acidhydrate of hexadecahedral decaborane [H B H -rzH O] with an epoxidehaving the structural formula,

wherein Y Y Y and Y, are hydrogen or monovalent radicals which areeither monomeric or polymeric in character. The product is convenientlyrecovered by precipitation as an insoluble salt; for example, the cesiumsalt, [Cs B H (OR) The hexadecahedral decaborane derivatives are usefulas detergents and as pigments or dyes.

This is a continuation-in-part of application Ser. No. 220,909, filedAug. 31, 1962 and now abandoned.

This invention relates to a process for preparing derivatives ofhexadecahedral decaborane and to compounds containing a hexadecahedraldecaborane structural unit.

Molecules containing ten boron atoms (decaboranes) can be made 'with twostructural arrangements; the recently discovered hexadecahedral (16sides) decaborane anion (B H and the well known cup shaped decaborane BH A description of the cup shaped decaborane can be found in Gould,Inorganic Reactions and Structure 130 (Revised edition 1962, HoltRinehart and Winston Inc.). The structural arrangement of thehexadecahedral decaborane anion is analogous to two square-basedpyramids having their bases spaced apart and facing each other with onebase rotated 45 relative to the other; each corner of each base is aboron atom and each boron atom is connected by a bond to the twoadjacent boron atoms of its base, the boron atom at the apex of itspyramid and the two closest boron atoms of the facing base. A hydrogenatom is attached externally to each boron in this symmetricalarrangement and the total structure carries an electric chargeequivalent to two electrons.

The similarity between the hexadecahedral and the cup shaped decaboranemolecules ends with the fact that they contain the same number of boronatoms. In addition to the structural differences described above, theirelemental makeup differs by the presence of four additional hydrogens inthe cup shaped decaborane molecule. With respect to property differencesthe cup shaped decaborane decomposes in water to form weak boric acid(pH about 5) and derivatives of cup shaped decaborane usually are activereducing agents for many metallic ions, do not form ions and aregenerally unstable. In contrast the hexadecahedral decaborane anion isstable in the presence of acid and in combination with hydrogen ionsforms a strong acid hydrate having the formula H B H -nl-l o (pH about2) and derivatives of hexadecahedral decaborane by virtue of thepresence of the decaborane alone are not reducing agents but form saltswith metallic and other cations, form strongly charged substituted ionsin aqueous 3,395,171 Patented July 30, 1968 solutions some of which havedetergency and coloring properties, and are generally stable.

Derivatives of cup shaped decaboranes have been prepared by reactionwith monooxyacycloalkanes in solutions of the monooxyacycloalkane. Thisreaction occurs at very slow rates, requiring as long as four weeks foroxol-anes and twenty hours for oxetanes at room temperature.

In the present invention a process for preparing derivatives ofhexadecahedral decaborane is provided which is more rapid and economicalthan the processes currently used to make derivatives of cup shapeddecaboranes. This process comprises reacting an acid hydrate ofhexadecahedral decaborane [H B H ynH O] with an epoxide having thestructural formula XL Ya It is thought that in this reaction one of theCO bonds of said epoxide is ruptured and the oxygen atom freed by theruptured bond attaches to a boron atom of the decaborane. In the epoxideeach of Y Y Y and Y, is hydrogen or a monovalent radical. Any epoxidewhich will react with benzene in the presence of aluminum chloride(catalyst) at a temperature less than about C. to form a substitutedbenzene of the type stituted hexadecahedral decaborane anions areproduced.

These substituted anions have the formula where OR corresponds to theepoxide utilized with the epoxy ring opened to form a monovalent ORradical which is bonded to a boron in the decaborane through the oxygen.The product is conveniently recovered by precipitation as an insolublesalt, for example, the cesium salt [Cs B H (OR) By varying the relativequantity of epoxide employed, other similar anions containing etherlikefunctions can be obtained having the general formula [B H ,,(OR),,]where y is a whole number from 1 to 4 preferably, and permissibly 5-10inclusive.

The substituted decaborane compounds of this invention can haveelectrical charges arising from the nature of the R groups in additionto the charge associated with the hexadecahedral decaborane. Forexample, R may bear carboxyl groups which, in ionic form, require thepresence of a cation. As a further illustration, R may bear basicgroups, e.g., NH which will form ionizable salts with acids. Cations andanions derived from R groups are considered to be part of these groupsand are included within the scope of the definition of R.

Solutions of the acid hydrate of hexadecahedral decaborane useful incarrying out the reaction of this invention can be in the form of anaqueous syrup in which water and the acid hydrate are present in aboutequal amounts by weight. However, no water is necessary for the presentprocess beyond that required to permit the hexadecahedral decaboraneanion to be in its acidic form.

In a preferred procedure this aqueous syrup is mixed with a solvent suchas glyme(ethylenegylcoldimethylether) to form a solution, and an epoxidein fluid form (i.e., this may be a liquid epoxide, or a solid epoxide insolution) is added slowly (usually dropwise) while maintaining thetemperature of the reaction mixture in the range of about 10 C. to about30 C. The reaction is practically instantaneous and is controlled by therate of addition of the epoxide and by regulating the solutiontemperature. With very highly reactive epoxides, temperature of 0 C. andeven lower may be necessary for reaction rate control whereastemperatures about 30 C. may be used to increase the reaction rate ofrelatively sluggish epoxides. Untried epoxides should be handled bystarting the reac' tion at a low temperature and gradually warming thereaction mixture until the desired reaction rate is achieved. Thereaction product is readily recovered by precipitation as an insolublesalt but any convenient recovery procedure such as extraction,distillation and the like can be used. Cesium in the form of CsF andCsOH is preferred as the precipitating agent.

Both liquid and solid epoxides can be utilized in this invention. Solidepoxides are conveniently dissolved in a solvent miscible with the acidhydrate solution to be used in order to facilitate contact between thereactants. Usually both reactants can be dissolved in glyme which isaccordingly a preferred solvent for practicing this invention. Otheruseful solvents include esters such as methyl acrylate and butylpropionate; dioxane and nitriles such as acetonitrile and benzonitrile.Preferably the solvent used is one in which the acid hydrate dissolvesreadily and is miscible with water. Most desirably the solvent shouldalso permit recovery of the product by a convenient method.

Epoxides having two or more oxirane groups can also be used in theprocess of this invention. In these epoxides the oxirane groups can bevicinal or can be separated by one or more intervening atoms. Usefulepoxides can be monoor polyfunctional, cyclic or acyclic. Polymericproducts are obtainable by using appropriate epoxides, that is, epoxideswith polymer forming functional groups or epoxides which are alreadypolymers containing one or more epoxy groups. Epoxides containingethylenic unsaturation sometimes react with the acid hydrate ofhexadecahedral decarborane to produce compounds in which -OR, theepoxide compound moiety, is saturated. Otherwise the oragnic portion ofthe reaction product usually corersponds to the epoxide reagent used,the epoxy group simply opening up and attaching to a boron of thehexadecahedral decaborane by an ether-like linkage.

In the epoxides useful in this invention Y Y Y and Y; can be the same ordifferent from each other and can be hydrogen or a radical such as anaromatic, aliphatic or alicyclic group or a heterocyclic group or can be:a functional group such as one of the functional groups listed below orone of the above-mentioned groups substituted with one or more of thefollowing functional groups:

In the above groups A is a monovalent organic radical preferablyhydrocarbon, of up to about 15 carbons, which can be alkyl, alkenyl,cycloalkyl, cycloalkenyl, aryl, alkaryl, aralkyl and the like. Any of YY Y and Y; may contain one or more epoxy groups and any two or more of YY Y and Y, can in combination represent an alicyclic or heterocyclicgroup.

Epoxides preferred for use in this invention are those having thestructural formula in which Y and Y have the meaning set forth above andin which Y and Y are functional groups such as those listed above orradicals containing such functional groups. Such epoxides in which thefunctional groups are polymer forming are particularly preferred. Thepolymer forming groups can be capable of forming addition polymers orcondensation polymers. Following reaction of epoxides containing polymerforming groups with the acid hydrate of hexadecahedral decaborane thepolymer can be produced by a conventional reaction.

Polymers containing the hexadecahedral decaborane unit can also beprepared by the process of the present invention by employing a polymercontaining an epoxy group, that is, an epoxide of the above structuralFormula 1 in which one or more of Y Y Y or Y, is a polymer radical, thatis, a radical formed by removing hydrogen from a polymer. The polymercan be an addition or a condensation polymer and is preferably a linearpolymer. Polyamides, polyesters and polyureas are preferred condensationpolymers, being very useful for the formation of fibers and films,coatings, finishes and insulation in applications where the presence ofthe decaborane anion is desirable.

The polymers of this invention contain a B group having ahex'adecahedral structure, usually as a component of each recurringunit. This group can be in the polymer backbone or in a pendant group.Thus, typical addition polymers have the recurring unit where W is adivalent organic radical containing an alkylene group attached to theoxygen in the formula, M, a and b are as defined below, and Z and/or Zis hydrogen or a monovalent radical such as -CN, COOH, -0H, halogen orhydrocarbon such as C to C alkyl, C to C alkenyl, or C to C aryl.Typical polymers can also contain the hexadecahedral B group as apendant group attached to the polymer stem by an ether-like linkage oras part of the polymer chain as in polymers with the recurring unit Lu.J

where M, a and b are as defined below and W is a divalent organicradical having an ethylene group (substituted or not) attached to theoxygens. For linear polymers the group -O-W O is a divalent organicradical obtained by reacting an epoxide disclosed above containing twoepoxide groups (as when one of Y Y Y or Y contains an epoxide group)with an acid hydrate of hexadecahedral decaborane according to thisinvention to open both of the epoxide groups. When the epoxide usedcontains more than two epoxide groups cross linking will usually resultif more than two of the epoxide groups are reactive under the conditionsused. Stated somewhat differently, W is a divalent organic radicalhaving the formula in H where 1 t t and L; are the same or different andcan be hydrogen or a monovalent organic radical sufficiently unreactivetoward epoxide groups to be capable of existence in the compound where trepresents each of t t t and t and W is any divalent organic radical.Polymers of this type can be prepared by reacting H B H -nH O with adiepoxide in accordance with the present invention.

All of the polymers referred to may have molecular weights comparable tothose of conventional and well known polymers. Persons skilled inpolymer chemistry are well aware of the reaction conditions which governpolymer formation and size and will have no difficulty in producing inaccordance with this invention polymers suitable for particularapplications and requiring specific properties in addition to thoseunique properties contributed by boron.

Other epoxides useful in this invention include the following:

Glycldol H2CCHCH2OH 0 --o ana -CEOD1-(3,4-epoxy'6methylcyclohexyI-methyladlpnte)3,4-epany-6-methy1cyclohexyl-methyl-3,4-epoxy-6- methylcyclohexanecarboxylate 3,4-epoxycyclohexane carbonltrlle Dlpentene dloxlde(llmonene dioxide) CH: O

1,2-epoxy-3phen0xy propane @wcmcrr-om \O/ Dipentene monoxide H3O CH;

Alpha-pinene oxide 1,2-ep0xy-3-ally10xy propane H10 CHCHrOCHrCH=CHR1,2-epoxy-3-(2-allylphenoxy) propane 1,2-epoxy-3-butoxy propane H20CHCHzOChHo @oomcncn,

1,2epoxy-3-(4-chlorophenoxy) propane Cl-OCHzCHCHg In the abovestructural formulas x is a Whole number, usually a large whole number,signifying the number of recurring structural groups in the formula of apolymer and p represents a phenyl group. I Salts of the derivatives ofhexadecahedral decaborane produced by the process of this invention canbe obtained Q Q by adding compounds capable of forming cations in the 0reaction product mixture or in a solvent miscible with and added to thereaction product mixture. These salts have the structural formula1,2-epoxy-3-(2,4-dlehlorophenoxy) propane 1,2-epoxy-3-ethoxypropane H OCHCH2OC2H5 O 1,2-epoxy-3-cyclohexoxypropane 1,2-ep0xy-3-(3-methylbutoxy) propane CH2CHCHaOCHzCHgCH(CH3):

3,4-epoxy-4methyl-2-pentanone ll CHa(l3--CH G O H:

3-phenyl-2,3-epoxy butyronltrlle where M is a cation; the B radical hasa hexadecahedral structure; OR is a monovalent organic substituentconnected to a boron atom by an ether-like linkage and corresponding tothe epoxide used in the reaction in its saturated form with the epoxyring opened; y is a whole number preferably from 1 to 4 and a and b arepositive Whole numbers of 1-3 inclusive, whose values are deter- O minedby the valence of M such that 1,2-epoxy'3-(3-methylphenoxy) propane@oomonom 1,2-epoxy-3-(2-methyl phenoxy) propane CHiCHCHjO CH31,2-epoxy'3-pentoxy propane CHzCHCHgO C5111] 1,2-ep0xy'3-propoxy propaneCHzCHCH2OCaH7 Phenyl methyl glycldlc ester3,4epoxy-2,5dlhydrothlophene-1,1-dloxlde b=%( valence of M) The ORgroups, when more than one is present, can be the same or different.Where R is a polymeric radical the above formula would represent arecurring unit in the polymer. (3H The corresponding compounds havingthe formula can be prepared by the same reactions under the same1,2-epoxy-3-methoxy propane 5O COl'ldltiOIlS utilizing an acid hydrateOf an eicosahedral decaborane. An acid hydrate of an eicosahedraldodecaborane (H2B 2H 2'flH2O) can be prepared by the procedure of US.Patent 3,169,044, the disclosure of which is hereby incorporated intothis specification.

The boron-containing group [B H (OR) in the 0 above formula is an anionin aqueous solution and behaves as a stable chemical entity inconventional reactions. By varying the amount of epoxide used in theprocess of preparation, y may be varied from 1 to 4 or to F 1o 9 1o s()2] [B H (OR) [B H (OR) and higher substituted hexadecahedral decaboraneanions of this type. Since these anions exhibit detergent properties inaqueous solu- 0 tion the compounds containing more than two (OR) 35groups are diificult to recover. Anions of the general formula areconveniently recovered as their insoluble salts such as the cesium saltCs B H (OR) the preferred compound being the salt Cs B H (OR)1,2-dlphenyl ethylene oxide M can be any cation which forms a salt withthe [B H (OR) in the reaction product mixture. 02 Where recovery of theboron derivative is not desired, as when it is going to be used insolution, the M can be any cation which produces a salt of the desiredsolubility with the anion produced. Exemplary cations include thefollowing: hydronium (H O ammonium (NHp'),

hydrazonium (NH NH N-substituted ammonium, N-substituted hydrazonium,aryldiazonium, pyridinium, quinolinium, sulfonium, phosphonium, metalamine, lithium, sodium, cesium, beryllium, barium, lanthanum, zirconium,vanadium, manganese, iron, cobalt, copper, zinc, mercury, aluminum,thallium, tin, lead, antimony; bismuth, silver or any other metal, ANH ANH A NH+, A N+, (ANHNH (A N-NH A S+ or A P+, where A is an organicradical bonded to the nitrogen, sulfur or phosphorus. The A groups arenot critical features of these cation groups. Substituents representedby A can be open-chain or closed-chain, saturated or unsaturated, or thegroups can be composed of heterocyclic rings of which the nitrogen,sulfur or phosphorus is a component, e.g., pyridine, quinoline,morpholine, hexamethyleneimine and the like. Preferably A, for reasonsof availability of reactants, represents a hydrocarbon group of up toabout 18 carbons.

The group M can be a Werner-type coordination complex, e.g., a metalamine such as [Ni(NH )3).] 2 4 2)a] l a).-.] and the like.

The products of this invention may be used in situ or may be recoveredand purified by any convenient means. Crystallization from aqueousethanol solutions is usually etfective. For products of limitedstability, solutions of the products can be treated with adsorptiveagents, e.g., activated charcoal or silica gel to adsorb the majorportion of the impurities.

To obtain compounds of this invention having two or more OR groups whichare unlike, the acid hydrate is reacted with one epoxide until thedesired number of substituents are introduced and the partiallysubstituted product is then reacted with a second epoxide. Theintermediate partially substituted product can, if desired, be isolatedprior to reaction with the second epoxide. The process can be repeatedwith a third epoxide or even further. Further modification of varioussubstituent groups can be accomplished by conventional methods to obtaincompounds having a broad range of OR groups.

Salts produced by the process of this invention are usually solids, manyof which dissolve in water. They vary in stability depending on thesubstituents and certain nitro and nitroso containing compounds aresensitive to shock and should be kept moist while handling. Others,including the halogen-substituted products and hydrocarbonsubstitutedproducts, are stable and can be stored for long periods withoutextraordinary care.

The process of this invention provides a unique method for introducing ahexadecahedral decaborane with its attendant properties into polymers.As pointed out above, this is accomplished by utilizing epoxides havingpolymers forming functional groups or other groups convertible into suchpolymer forming groups. The process is also useful for introducinghexadecahedral decaborane into a wide variety of other compounds forapplications where a high boron content is desirable. Many of thecompounds have detergent properties and some are colored permittingtheir use as pigments or dyes. The decaborane of the products of thisinvention possess an aromatic character and undergoes reactions in amanner resembling benzene, that is, it will react with reagents to addsubstituents which are capable of bonding to a carbon of an aromaticnucleus such as benzene, naphthalene, toluene, etc. Thus, compounds oranions produced by this invention and in which the decaboranes hydrogenatoms are not completely replaced by OR groups, can be reacted with thenumerous reagents suitable for reaction with an aromatic compound toproduce a large variety of compounds.

The process of this invention and products produced thereby areillustrated in the following examples. Preparation of an acid hydrate ofhexadecahedral decaborane from commercially available cup shapeddecaborane (B H is shown in Example 1.

EXAMPLE 1 A. Preparation of a decaboryl bis(dialkyl sulfide) A reactionvessel having a capacity of about 365 g. of water is charged with 0.79g. of cup shaped decaborane, cooled in liquid nitrogen, and thenevacuated to a pressure of 10 microns of mercury. Approximately 21 g. ofmethyl sulfide is condensed onto the decaborane in the reaction vessel.The reaction vessel is closed, allowed to warm to room temperature andstand for 4 days. During this time, 6.6 millimoles of hydrogen isevolved. The reaction vessel is opened and excess methyl sulfide isremoved by distillation, leaving a practically quantitative yield ofwhite solid residue of B H -2(CH S. The compound is recrystallized fromethyl acetate and it melts at 122-124 C. The compound is calledbis(dimethyl sulfide)decaborane( 10).

The above procedure is equally operable with other organic sulfides.

B. Preparation of M B H (where M is NH Bis(dimethylsulfide)decaborane(l0) (8.5 g.) is mixed with 50 ml. of liquid ammoniaand stirred in a roundbottom reaction vessel for one hour with thevessel being cooled to a temperature of about 50" C. by partialimmersion in a bath of a mixture of solid carbon dioxide and acetone.The cooling bath is then removed and the excess ammonia is allowed toevaporate with stirring. The remaining traces of ammonia are removed bysubjecting the residue to a high vacuum (0.01 mm. of mercury) at 25 C.There is obtained 5.6 g. of solid residue which is virtually aquantitative yield of diammonium hexadecahedral decaborane (NHQ B H C.Preparation of H B H -nH O A solution of (NHQ B H obtained in part B in30 ml. of water is passed through a 0.5 inch diameter chromatographycolumn containing ml. of a commercial acidic ion exchange resin(Amberlite IR 1 20=H). The water eflluent is clear, colorless andacidic. The column is rinsed with more water until the effiuent is nolonger acidic and the water fractions are combined. Evaporation of thecombined aqueous solutions under reduced pressure (1 mm. of mercury) ata temperature of about 40 C. leaves a yellow viscous liquid which is theacid hydrate of hexadecahedral decaborane (H B H -nH o).

EXAMPLE 2 A solution of 2.0 g. (0.013 mole) of diammonium hexadecahedraldecaborane in 10 ml. of Water is passed through an Amberlite IR -'H ionexchange column to produce the acid hydrate (H B H -n I-I O). Water isevaporated in vacuum at 25 C. and the oily residue dissolved in 20 ml.of glyme. A solution of 2.4 g. (0.026 mole) of epichlorohydrin in 10 ml.of glyme is added dropwise. The instantaneous reaction is cooled in anice bath. The solvent is evaporated in vacuum and the residue dissolvedin ethanol. Addition of 3.9 g. (0.026 mole) of CsF dissolved in 10 ml.of glyme results in the formation of a light yellow precipitate.

Analysis shows that one molecule of solvent has also reacted to give CsB I-I (OCH CH CH C1) (OCH CHOCH in which the B has a hexadecahedralstructure.

Calcd: C, 13.8; H, 4.06; B, 20.9; C1, 6.8. Found: C, 13.13; H, 4.03; B,22.01; Cl, 4.03.

EXAMPLE 3 To a solution of the acid hydrate of hexadecahedral decaboranein glyme prepared in Example 1 about 3.1 g. (0.026 mole) of styreneoxide is added while cooling in an ice bath. The reaction is practicallyinstantaneous at 37 C. The solvent is evaporated in vacuum to give adark brown gum. This residue is dissolved in 20 ml. of ethanol and 3.9g. (0.026 mole) of CsF dissolved in ethanol is in which the B has ahexadecahedral structure.

Calcc1: C, 30.78; H, 4.17; B, 17.32. Found: C, 29.32; H, 4.36; B, 18114.

EXAMPLE 4 A solution of 2.1 g. (0.013 mole) of dicyclopentadiene dioxidedissolved in 10 ml. of glyme is added dropwise to a 20 ml. solution ofthe acid hydrate of hexadecahedral decaborane inethyleneglycoldimethylether prepared as in Example 1. The solutionbecomes hot (glyme reflux) and an orange color develops. The solution isthen allowed to cool to room temperature and the solvent is evaporatedat reduced pressure. The residual tar is dissolved in ethanol and asolution of 3.9 g. (0.026 mole) of CsF added. An orange precipitateforms and is isolated. Elemental infrared analyses show the product isin which the B has a hexadecahedral structure.

Calcd: C, 21.80; H, 4.36; B, 19.60. Found: C, 22.54; H, 5.44; B, 19.80.

EXAMPLE This example illustrates the following reaction:

O -2 II nwnlo GIIZCHZCHZO C 0 (CH (11+);

hydrolysis CsF The procedure of Example 3 is followed and the ultimateproduct anion ('4) is recovered by precipitation and identified byelemental and infrared analyses as the cesium saltCS2B10H8(OCH2CH2CH2OH) in the B has a hexadecahedral structure.

Calcd: C, 7.87; H, 3.5; B, 23.5. Found: C, 7.70; H, 3.27; B, 18.48.

EXAMPLE 6 The following reaction is carried out:

'A solution of 15.4 g. (0.10 mole) of (NHQ B H (as produced in Example1B) in 40 ml. of water is passed through an Amberlite :IR 120- H ionexchange column to produce the acid hydrate of hexadecahedral decaboraneH B H -nH O. Water is evaporated from the HgBmH "H2O solution in vacuumat C. to give a residue of about 20 ml. volume. The acid residue isdissolved in 60 ml. of glyme and 26.8 g. (0.20 mole) of3,4-epoxy-2,5-dihydrothiophene-L l-dioxide added dropwise.

The glyme is evaporated in vacuum and the residue dissolved in 60 ml. ofethanol. A solution of 30.4 g. (0.20

12 mole) of cesium fiuonide in '60 ml. of ethanol is added to in whichthe B has a hexadecahedral structure. The product is recrystallized froman ethanol-water mixture.

A solution of 15.4 g. (0.10 mole) of (NHQ B H as produced in Example 1Bin 40 ml. of water is passed through an Amberlite IR -H ion exchangecolumn to produce the acid hydrate H 'B H -nH O. Water is evap oratedfrom the H BmH -nH o solution in vacuum at 20 C. to give a residue ofabout 20 ml. volume. The acid residue is dissolved in 60 ml. of glymeand 22.8 g. (0.20 mole) of 3,4-epoxy-4-methyl-2-pentanone addeddropwise. The glyme is evaporated in vacuum and the residue dissolved in60 ml. of ethanol. A solution of 30.4 g. (0.20 mole) of cesium fluoridein 60ml. of ethanol is added to precipitate in which the B has ahexadecahedral structure. The product is recrystallized from anethanol-water mixture.

EXAMPLE 8 This example illustrates the reaction of a polymeric epoxidewith decahydrodecaborate acid hydrate.

CHzOCHzCH-CH2 (CH2CH); CHzOCHzCHzCHzOBmHs-O CHaCHzC 0 0 CE; I

OH-CH l- L (0st) D .1 which was characterized by elemental and infraredanalyses to have the structure shown.

Calcd: C, 23.5; H, 4.9; B, 17.6. Found: C, 23.13; H, 5.3; B, 16.2.

EXAMPLE 9 OsF 2CH3CHCH7 HzBmHwnHzO CSflBroHflOCaH-rh] The reaction isconducted accordin to the procedure of Example 3 in glyme at atemperature of 30 C. and the product recovered as its cesium salt.Direction of opening of the epoxide ring was shown to occur at both the1 and 2 position by hydrolysis of and identification of both n-propyland isopropyl alcohol as derivatives.

13 EXAMPLE 10 1| COCaHs H BmHm-nHzo 0 ii B 011.- o--o 0 0m.

The procedure of Example 3 is followed at a temperature of 30 C. inglyme. The product (is precipitated and recovered as its cesium salt.

EXAMPLE 11 CsF The reaction was carried out in methyl cyanide accordingto the procedure of Example 3 at a temperature of 55 C. and the productanion precipitated and recovered as its cesium salt.

Calcd: C, 30.78; H, 4.17; B, 17.32. Found: C, 29.32; H, 4.36; B, 18.14.

EXAMPLE 12 (EN (EN OS BmHs -O 2 Ha ro wflHzo C 2 A solution of 15.4 g.(0.10 mole) of (NH B H (as produced in Example 1B) in 40 ml. of water ispassed through an Amberlite IR 120-H ion-exchange column to produce theacid hydrate H B H -nH O. Water is evaporated from the H B H -nl-l osolution in vacuum at a temperature of less than 20 C. to give a residueof about 20 m1. volume. The acid residue is dissolved in 60 ml. of glymeand 24.6 g. (0.20 mole) of 3,4-epoxycyelohexane carbonitrile addeddropwise at less than 30 C. Glyme is evaporated in vacuum and theresidue dissolved in 60 ml. of ethanol. A solution of 30.4 g. (0.20mole) of cesium fluoride in 60 ml. of ethanol is added to precipitateCsz B1011. 0

in which the B has a hexadecahedral structure. The product isrecrystallized from an ethanol-water mixture.

A solution of 15.4 g. (0.10 mole) of (NHQ B H as produced in Example 1Bin 40 ml. of water is passed through an Amberlite IR 120-H ion-exchangecolumn to produce the acid hydrate H B H -nH o. Water is evaporated fromthe H B H -nH O (solution) in vacuum at a temperature of less than 20 C.to give a residue of about 20 m1. volume. The acid residue is dissolvedin 60 ml. of glyme and 30.0 g. (0.20 mole) of 1,2-epoxy-3-phenoxypropane added dropwise at less than 30 C. Glyme is evaporated invacuum and the residue dissolved in 60 ml. of ethanol. A solution of 30g. (0.20 mole) of cesium fluoride in 60 ml. of ethanol is added toprecipitate CSZ[B1OH8(OCH2CH2CHZO)2] in the B10 has a hexadecahedralstructure. The product is recrystallized from ethanol-water mixture.

EXAMPLE 14 H30 CH3 CSF CS2 io e 2 HzBmHm-TZHzO r H O CH: H30 CH2 2 Asolution of 15.4 g. (0.10 mole) of (NH B H as produced in Example 1B in40 ml. of water is passed through an Amberlite IR -H ion-exchange columnto produce the acid hydrate H B H -nH O. Water is evaporated from the HB H -nH O (solution) in vacuum at a temperature of less than 20 C. togive a residue of about 20 ml. volume. The acid residue is dissolved in60 ml. of glyme and 30.4 g. (0.20 mole) of dipentene monoxide addeddropwise at less than 0 C. Glyme is evaporated in vacuum and the residuedissolve in 60 ml. of ethanol. A solution of 30.4 g. (0.20 mole) ofcesium fluoride in 60 ml. of ethanol is added to precipitate CS7 B mHs-0 Hso \CH2 2 in which the B has a hexadecahedral structure. The productis not recrystallized.

EXAMPLE 15 A solution of 15.4 g. (0.10 mole) of (NHQ B H as produced inExample 1B in 40 ml. of water is passed through an Amberlite IR l20-Hion-exchange column to produce the acid hydrate H B H -nH O. Water isevaporated from the H B H -nH O (solution) in vacuum at 20 C. to give aresidue of about 20 ml. volume. The acid residue is dissolved in 60 ml.of glyme and 33.6 g. (0.20 mole) of l,2-epoxy-3-(4-chlorophenoxy)propaneadded dropwise. The glyme is evaporated in vacuum and the residuedissolved in 60 ml. of ethanol. A solution of 30.4 g. (0.2 mole) ofcesium fluoride in 60 ml. of ethanol is added to precipitate in whichthe B has a hexadecahedral structure.

EXAMPLE 16 CsF ZCHzCHzCI-DOCH; HaBwHwnHrO O CSzEBmHKOCHzCHzCHzOCH3)2] Asolution of 15.4 g. (0.10 mole) of (NHg B H as produced in Example 1B in40 ml. of Water is passed through an Amberlite IR 120-H ion-exchangecolumn to produce the acid hydrate H B H -nH O. Water is evaporated fromthe H B H -nH o solution in vacuum at 20 C. to give a residue of about20 ml. volume. The acid residue is dissolved in 60 ml. of glyme and 17.6g. (0.20 mole) of 1,2-epoxy-3-methoxypropane added dropwise. The glymeis evaporated in vacuum and the residue dissolved in 60 ml. of ethanol.A solution of 30.4 g. (0.20 mole) of cesium fluoride in 60 ml. ofethanol is added to precipitate CS [B H (OCH cH CH OCH in which the Bhas a hexadecahedral structure.

EXAMPLE 17 A solution of 15.4 g. (0.10 mole) of (NHQ B H as produced inExample 1B in 40 ml. of water is passed through an Amberlite IR 120Hion-exchange column to produce the acid hydrate H B H -nH o. Water isevaporated from the H B H -nH O in vacuum at 20 C. to give a residue ofabout 20 ml. volume. The acid residue is dissolved in 60 ml. of glymeand 38.4 g. (0.20 mole) of phenylmethylglycidic ester added dropwise.The glyme is evaporated in vacuum and the residue dissolved in 60 ml. ofethanol. A solution of 30.4 g. (0.20 mole) of cesium fluoride in 60 ml.of ethanol is added to precipitate in which the B has a hexadecahedralstructure. The product is recrystallized from an ethanol-water mixture.

What is claimed is:

1. A process for preparing derivatives of hexadecahedral decaboranewhich comprises contacting an acid hydrate of hexadecahedral decaboranehaving the formula H B H -nH O with an epoxide having the structuralformula,

in which Y Y Y and Y; are individually selected from the group ofhydrogen and a monovalent radical such that the epoxide is one which iscapable of reacting with benzene in the presence of an aluminum chloridecatalyst at a temperature of less than 100 C.

2. The process of claim 1 in which the reaction is carried out in anaqueous solution of the acid hydrate of hexadecahedral decaborane.

3. The process of claim 2 in which at least one of Y and Y is an organicradical with a functional group selected from the group of wherein A isa monovalent organic radical of up to about carbon atoms.

16 4. The process of claim 2 in which Y is a monovalent polymericradical having the structural formula,

02120 GHQ- wherein: Z and Z' are individually selected from the groupconsisting of hydrogen, cyano, carboxylic, hydroxyl, halogen, C to Calkyl, C to C alkenyl and C to C aryl; and x is a large whole number.

5. The process of claim 4 in which Y is a monovalent radical of acondensation polymer.

6. The process of claim 4 in which Y is a monovalent radical of anaddition polymer.

7. The process of claim 1 in which the epoxide is styrene oxide.

8. The process of claim 1 wherein the epoxide is ethylene oxide.

9. The process of claim 1 wherein the epoxide is propylene oxide.

10. The process of claim 1 wherein the epoxide is dicyclopentadienedioxide.

11. A linear synthetic organic addition polymer characterized by therecurring structural unit,

2 Z l (5, l l

wHp b X wherein: Z and Z are individually selected from the groupconsisting of hydrogen, cyano, carboxylic, hydroxyl, halogen, C to Calkyl, C to C alkenyl and C to C aryl; the B radical has ahexadecahedral structure; M is a cation which forms a salt with theradical m m-i HT a and b are whole numbers of 1-3 inclusive whose valuesare determined by the valence of M and x is a whole number.

12. A linear synthetic organic condensation polymer characterized by therecurring structural unit References Cited UNITED STATES PATENTS 5/1962Shokel et a1. 260-2 6/1963 Aitandilian et al. 260-2 WILLIAM H. SHORT,Primary Examiner.

T. PERTILLA, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3,395,171 July 30 1968 William C. Drinkard, Jr.

It is certified that error appears in the above identified patent andthat said Letters Patent are hereby corrected as shown below: Column 15,lines 36 to 39, the formula should appear as shown below:

0 W Y Y Signed and sealed this 3rd day of February 1970 (SEAL) Attest:

WILLIAM E. SCHUYLER, JR.

Commissioner of Patents Edward M. Fletcher, Jr.

Attesting Officer

